JPS60241281A - Method of oxidizing solid substance - Google Patents

Method of oxidizing solid substance

Info

Publication number
JPS60241281A
JPS60241281A JP60045024A JP4502485A JPS60241281A JP S60241281 A JPS60241281 A JP S60241281A JP 60045024 A JP60045024 A JP 60045024A JP 4502485 A JP4502485 A JP 4502485A JP S60241281 A JPS60241281 A JP S60241281A
Authority
JP
Japan
Prior art keywords
oxidation
niobium
cerium
oxygen
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP60045024A
Other languages
Japanese (ja)
Other versions
JPH0638524B2 (en
Inventor
エルンスト‐エベルハルト・ラツタ
マリア・ロネイ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Business Machines Corp
Original Assignee
International Business Machines Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Publication of JPS60241281A publication Critical patent/JPS60241281A/en
Publication of JPH0638524B2 publication Critical patent/JPH0638524B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
    • H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
    • H01L21/02244—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of a metallic layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising
    • C—CHEMISTRY; METALLURGY
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    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C8/10—Oxidising
    • C23C8/12—Oxidising using elemental oxygen or ozone
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Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、金属や半導体などの物質上に酸化物層を調製
することに関係しており、さらに具体的にいえば、かか
る物質を室温に近い温度で触媒酸化して、集積回路装置
の製造に有用な処理中間体上に高品質の極薄の絶縁材料
を形成することに関係するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention relates to the preparation of oxide layers on materials such as metals and semiconductors, and more specifically to the preparation of oxide layers on materials such as metals and semiconductors, and more specifically to the preparation of oxide layers on materials such as metals and semiconductors. It involves catalytic oxidation at temperatures close to , to form high quality ultrathin insulating materials on processing intermediates useful in the manufacture of integrated circuit devices.

［開示の概要］ ニオブ金属の表面に一層または数層のセリウム単分子層
を配列すると、室温でニオブの酸化触媒として働き、触
媒のパターン付けによって構成できる非常に薄く非常に
高品質の絶縁層ができる。SUMMARY OF THE DISCLOSURE Arranging one or several monolayers of cerium on the surface of niobium metal acts as an oxidation catalyst for niobium at room temperature, creating a very thin and very high quality insulating layer that can be constructed by patterning the catalyst. can.

セリウムの存在によって促進されて、６．６Ｘ１０−’
Ｐａという低い圧力でかなりの量のＮｂ、Ｏ。Facilitated by the presence of cerium, 6.6X10-'
A considerable amount of Nb and O at a low pressure of Pa.

が生成される。この触媒作用は、酸化中にセリウムの原
子価が３価から４価に変わることに関係している。セリ
ウム酸化の下でのＮｂ２Ｏ５形成の反応速度論は２段階
である。is generated. This catalytic effect is related to the change in the valence of cerium from trivalent to tetravalent during oxidation. The kinetics of Nb2O5 formation under cerium oxidation is two-step.

第１段は、イオン拡散によって限定される速い成長であ
る。The first stage is fast growth limited by ion diffusion.

第２段は、電子トンネリングによって限定されるゆっく
りした成長である。The second stage is slow growth limited by electron tunneling.

セリウムの代りに使用できるその他の触媒作用をもつ希
土類は、テルビウムとプラセオジムである。ニオブの代
りに使用できるその他の基板材料は、アルミニウム、八
ツニウム、シリコン、タンタルまたはそれらの酸化可能
な合金である。Other catalytic rare earths that can be used in place of cerium are terbium and praseodymium. Other substrate materials that can be used in place of niobium are aluminum, octunium, silicon, tantalum or oxidizable alloys thereof.

［従来の技術］ 近年、多結晶ニオブの室温酸化が、超伝導ジョセフソン
接合中のトン半ル障壁材料として使用できることから、
注目を集めている。主な関心は、大きな過剰電流の原因
と考えられる亜酸化物の存在の直接の証拠を見つけるこ
とであった。Ｘ線光電子分光分析（ＸＰＳ）の研究から
、ニオブの酸化は、最初に酸素を急速に吸収し、次にＮ
ｂＯとＮｂＯ２の薄い層が形成され、続いて大きな酸素
暴露で表面にＮｂ２ｏ５が形成されることを特徴とする
ことがわかった。ニオブの低次酸化物は、Ｎｂ２Ｏ５と
は対照的な低い絶縁特性を示す。サンズとホフマンは、
Ｎｂ２Ｏ，形成の反応速度をめた。[Prior Art] In recent years, room-temperature oxidation of polycrystalline niobium can be used as a ton-half barrier material in superconducting Josephson junctions.
It is attracting attention. The main interest was to find direct evidence of the presence of suboxides, which could be responsible for the large excess current. From X-ray photoelectron spectroscopy (XPS) studies, niobium oxidation first rapidly absorbs oxygen, then N
It was found to be characterized by the formation of a thin layer of bO and NbO2, followed by the formation of Nb2o5 on the surface with large oxygen exposure. Lower oxides of niobium exhibit poor insulating properties in contrast to Nb2O5. Sands and Hoffman
The reaction rate of Nb2O formation was estimated.

それは、超高真空（ＵＨＶ）条件下で乾燥酸素中で対数
成長法則に従い、１０’Ｌ　（ＩＬ＝１０−６Ｔｏｒｒ
、５ｅｃ＝　１　、３２　Ｘ　１０”′４Ｐａ、５ｅｃ
）の酸素暴露後に０．２ナノメートルの厚さに達する。It follows a logarithmic growth law in dry oxygen under ultra-high vacuum (UHV) conditions and grows to 10'L (IL=10-6 Torr
, 5ec= 1, 32 X 10"'4Pa, 5ec
) reaches a thickness of 0.2 nanometers after exposure to oxygen.

ジェニ・エム・サンズ及びニス・ホフマン、ジャーナル
・オブ・レス−コモン・メタルズ１巻２９、ページ３　
１　７　（Ｊ＋ｏｆ　ｔｈｅ　Ｌｅｓｓ−Ｃｏｍｍｏｎ
　Ｍｅｔａｌｓ、Ｖｏｌｕｍｅ９２、　ｐ、３１７（１
９８３））を参照のこと。Jenni M. Sands and Nis Hoffman, Journal of Less-Common Metals, Volume 1, 29, Page 3
1 7 (J+of the Less-Common
Metals, Volume 92, p, 317 (1
See 983)).

セリウムの表面酸化のＸＰＳと芯型子エネルギー損失分
光分析の研究からは、最初にＣｅ２Ｏ３が形成され続い
て表面にＣｅＯ２の簿い層ができることが示唆される。XPS and core energy loss spectroscopy studies of surface oxidation of cerium suggest that Ce2O3 is first formed followed by a thin layer of CeO2 on the surface.

水蒸気による酸化では３価の酸化物しか形成されない。Oxidation with water vapor only forms trivalent oxides.

ビー・イー・コエル等、ジャーナル・オブ・エレクトリ
ック・スペクトロスコピー・リレーテシド・フエノミナ
（Ｊ、Ｅ］、ｅｃｔｒ。B.E. Coel et al., Journal of Electrical Spectroscopy Relatecid Phenomina (J,E), ectr.

５ｐｅｃｔｒ、Ｒｅ１．Ｐｈｅｎ、Ｖｏｌ、　２１　、
ｐ、３１　（１９８０）　）及びジー・ストラツサー及
びエフ・ピー・ネツアー、ジャーナル・オブ・バキュー
ム・サイエンス・アンド・テクノロジー（Ｊ、Ｖａｃ、
Ｓｃｉ、Ｔｅｃｈ、、５ｅｃｔｉｏｎ　Ａ、、Ｖｏｌ、
２、ｐａｇｅ８２６、Ａｐｒｉｌ−Ｍａｙ　１９８４）
を参照のこと。5pectr, Re1. Phen, Vol. 21,
p. 31 (1980)) and G. Stratzer and F.P. Netzer, Journal of Vacuum Science and Technology (J. Vac.
Sci,Tech,,5section A,,Vol.
2, page 826, April-May 1984)
checking ...

室温で空気に暴露したとき固有酸化物を形成する金属は
、アルミニウムやニオブを含めて沢山ある。しかし、本
発明のもとになった実験研究より前には、固体の触媒酸
化は知られていない。Many metals, including aluminum and niobium, form intrinsic oxides when exposed to air at room temperature. However, prior to the experimental work that gave rise to the present invention, catalytic oxidation of solids was unknown.

さらに、Ｘ線光電子放射分光分析（ｘｐｓ）の研究から
、薄いアルミニウム、薄いイツトリウムまたはマグネシ
ウム、イツトリウムまたはエルビウム保護層を使うと、
ニオブの空気酸化を抑えられることがわかっている。Additionally, X-ray photoemission spectroscopy (XPS) studies have shown that using thin aluminum, thin yttrium or magnesium, yttrium or erbium protective layers;
It is known that air oxidation of niobium can be suppressed.

絶縁酸化物層を調製するための技術には、一般に高温が
必要であるが、温度が高いと、汚染物質の拡散やドーパ
ントの最適範囲を越える拡散など他の問題を引き起こす
ので、望ましくないことがわかっている。集積回路に大
きな関心が集中しているため、多数の研究所で酸化物の
研究が行なわれたが、有意な絶縁層の室温酸化が実現で
きるとの知識はもたらされず、もちろんかかる酸化を実
施するための現実的知識も、実際の触媒や方法の選択に
関する知識ももたらされなかった。半導体集積回路やそ
の他の集積回路に必要な酸化物層には、依然として高温
が必要であった。Techniques for preparing insulating oxide layers generally require high temperatures, which may be undesirable because they cause other problems such as diffusion of contaminants or diffusion of dopants beyond the optimal range. know. The great focus on integrated circuits has led to research on oxides in numerous laboratories, but this has not led to the knowledge that significant room temperature oxidation of insulating layers can be achieved, and of course it is difficult to carry out such oxidations. No knowledge of practical methods or selection of catalysts or methods was provided. Oxide layers required for semiconductor integrated circuits and other integrated circuits still required high temperatures.

白金、ロジウム、パラジウム４セリウムなどある種の触
媒、特に白金は、自動車産業で排気ガスの浄化に使われ
ることが普通になっている。排気ガスの触媒反応は高温
で起こり、気体成分しか関係しない。例えば、米国特許
第４’　２７４９８１号を参照のこと。Certain catalysts, especially platinum, such as platinum, rhodium, and palladium-tetracerium, are commonly used in the automotive industry to purify exhaust gases. Catalytic reactions in exhaust gas occur at high temperatures and involve only gaseous components. See, eg, US Pat. No. 4'274,981.

ある種の希土類や金属は、触媒特性をもつことが知られ
ている。ゲルマニウム、セリウム、トリウム、マンガン
、ニオブ、クロム、プラセオジウム、イツトリウム、ジ
ルコニウム、ルテニウム、ガリウム、スズ、インジウム
、銅、ランタン、タンタル、タングステンなどが、酸化
を推進するものとして記載されている。例えば、米国特
許第４００１３１７号を参照のこと。Certain rare earths and metals are known to have catalytic properties. Germanium, cerium, thorium, manganese, niobium, chromium, praseodymium, yttrium, zirconium, ruthenium, gallium, tin, indium, copper, lanthanum, tantalum, tungsten, and others have been described as promoting oxidation. See, eg, US Pat. No. 4,001,317.

先行技術は、気体物質及び有機物質に関するものであり
、半導体の製造に使用される加工中間体や固体の酸化は
扱っていない。The prior art concerns gaseous and organic materials and does not deal with the oxidation of processing intermediates or solids used in the manufacture of semiconductors.

［発明力ｒ解決しようとする問題点］ 本発明の目的は、かかる酸化反応で通常必要な圧力と温
度の加工パラメータよりはるかに会い温度で材料を触媒
酸化して、有用な絶縁層を調製することである。[Problems to be Solved] It is an object of the present invention to catalytically oxidize materials at temperatures far exceeding the pressure and temperature processing parameters normally required for such oxidation reactions to prepare useful insulating layers. That's true.

［問題点を解決するための手段］ 本発明の一つの特徴は、表面酸化によって原子価が３価
から４価に変わる、セリウムやその他の希土類元素のい
くつかの単分子層を使って、高品質の滑らかで薄い酸化
物層をもたらすことである。[Means for Solving the Problems] One feature of the present invention is to use several monolayers of cerium and other rare earth elements whose valence changes from trivalent to tetravalent through surface oxidation. The quality is to yield a smooth and thin oxide layer.

本発明の一つの利点は、高品質の絶縁層の有効パターン
を、高温を必要とせずに、触媒パターンがそのまま受け
容れできるかまたは容易に取り除けるような形で低コス
トで提供することである。One advantage of the present invention is that it provides an effective pattern of high quality insulating layers at low cost, without the need for high temperatures, and in a form where the catalyst pattern can be accepted as is or easily removed.

本発明の上記その他の目的、特徴及び利点を明らかにす
るため、添付の図面に図示した如き本発明の良好な実施
例についてより詳しく説明する。In order to make these and other objects, features and advantages of the present invention clearer, preferred embodiments of the invention will now be described in more detail as illustrated in the accompanying drawings.

［実施例］ セリウムをニオブ金属性の基板表面に一層ないし数層の
単分子層として配列すると、室温でニオブ基板の酸化触
媒として働き、非常に高品質の薄い絶縁層ができる。他
のある種の触媒、一般には酸化反応中に原子価が増す希
土類も、また他のある種の基板材料、一般には酸化可能
な金属または半導体も使用できる。EXAMPLE When cerium is arranged in one or several monolayers on the surface of a niobium metallic substrate, it acts as an oxidation catalyst for the niobium substrate at room temperature, resulting in a thin insulating layer of very high quality. Certain other catalysts, generally rare earths whose valence increases during the oxidation reaction, can also be used, as well as certain other substrate materials, generally oxidizable metals or semiconductors.

相当の量のＮｂ２Ｏ，が、セリウムの存在によつ・　て
促進されて６．６Ｘ１０””Ｐａという低い圧力で形成
される。この触媒作用は、酸化中にセリウムの原子価が
３価から４価に変わることに関係するものである。酸化
されたセリウムの下でのＮｂ２Ｏ，の反応速度論は、２
段階である。Significant amounts of Nb2O, are formed at pressures as low as 6.6 x 10''Pa, facilitated by the presence of cerium. This catalytic effect is related to the change in the valence of cerium from trivalent to tetravalent during oxidation. The reaction kinetics of Nb2O, under cerium oxide is 2
It is a stage.

第１段は、イオン拡散によって限定される速い成長であ
る。The first stage is fast growth limited by ion diffusion.

第２段は、電子のトンネリングによって限定されるゆっ
くりした成長である。The second stage is slow growth limited by electron tunneling.

非常に薄いセリウムの保護層でも、ニオブ金属の酸化を
促進する。例えば、僅か２００Ｌの酸素暴露後に４．５
ｎｍのＮｂ２Ｏ５が酸化されたセリウムの下に形成され
、より低次の酸化物は検出されない。Even a very thin protective layer of cerium promotes oxidation of the niobium metal. For example, after only 200 L of oxygen exposure, 4.5
nm of Nb2O5 is formed under the oxidized cerium, and no lower oxides are detected.

集積回路製造の加工中間体を生成する方法として一般に
有用な本発明を実施するための、有利な出発材料は、適
当な基板に蒸着させたニオブである。加工は一般に超高
真空（ＵＨＶ）系で行なう。A preferred starting material for carrying out the present invention, which is generally useful as a method for producing processing intermediates for integrated circuit manufacturing, is niobium deposited on a suitable substrate. Processing is generally performed in an ultra-high vacuum (UHV) system.

ニオブ膜とセリウム保護層を３００’にで蒸発させて酸
化させ、第１図に示した加工中間体を形成する。基板の
金属ニオブ１（これをさらに別の基板に載せてもよい）
は酸化されてＮｂ、Ｏ，層２を含むようになり、セリウ
ムの薄い触媒層は酸化されてＣｅ　Ｏ２＋　Ｃｅ　２０
３　Ｍ　３になっている。The niobium film and cerium protective layer are evaporated and oxidized at 300' to form the processed intermediate shown in FIG. Metal niobium 1 on the substrate (this may be placed on another substrate)
is oxidized to contain Nb, O, layer 2, and the thin catalyst layer of cerium is oxidized to form Ce O2+ Ce 20
It has become 3M3.

触媒の酸化は、ｘｐｓでＭｇＫα励起（１２５２，６ｅ
Ｖ）を使ってその場で表面にほぼ垂直に観測方法で分析
した、後からの分析で確認されている。The oxidation of the catalyst was performed using MgKα excitation (1252,6e
This was confirmed by subsequent analysis using an observation method almost perpendicular to the surface on the spot using V).

まず約２５ｒ＋＋＋＋のニオブを蒸着する。そのＸＰＳ
スペクトルはクリーンな金属の電子レベルしか示さない
。結合エネルギーが２０２．３ｅＶのＮｂ５ｄ、、□ピ
ークと２０５．１ｅＶのＮｂ５ｄ、、□ピークのプロッ
トを第２図の曲線（ａ）に示す。６゜６Ｘ１０−ＧＰａ
の純粋な酸素に２０分間暴露した後、Ｎｂ５ｄレベルは
第２図の曲線（ｂ）にみられるように、少量の低次Ｎｂ
酸化物の形成のみを示す。First, approximately 25r++++ of niobium is deposited. That XPS
The spectrum shows only clean metal electron levels. A plot of the Nb5d, , □ peak with a binding energy of 202.3 eV and the Nb5d, , □ peak with a binding energy of 205.1 eV is shown in curve (a) in FIG. 6゜6X10-GPa
After 20 minutes of exposure to pure oxygen of
Only oxide formation is shown.

適当な基板上に２５ｎｍのニオブを蒸着し、ニオブの頂
面に０．６ｎｍのセリウムを蒸着する。第３図の曲線（
ａ）は、この時点でのＮｂ５ｄのレベルを示したもので
ある。６．６Ｘ１０−’Ｐａの純粋酸素に２０分間暴露
した後、第３図の曲線（ｂ）に示すようにかなりの量の
ニオブ酸化物が形成される。できたニオブ酸化物は、Ｎ
ｂ５ｃルベルが５゜１ｅＶ化学シフトするのが特徴であ
る。このＮｂ３　ｄ　５／□で２０７　、４　ｅ　Ｖ、
　Ｎ　ｂ　３　ｄ　Ｓ／２で２１０゜２’ｅＶの結合エ
ネルギーは、Ｎ　ｂ　２０　ｓの特徴である。酸化物の
厚さｔａｘは、方程式１のように推定できる。Deposit 25 nm of niobium on a suitable substrate and 0.6 nm of cerium on top of the niobium. The curve in Figure 3 (
Panel a) shows the level of Nb5d at this point. After 20 minutes of exposure to 6.6 x 10-'Pa of pure oxygen, a significant amount of niobium oxide is formed, as shown in curve (b) of Figure 3. The resulting niobium oxide is N
It is characterized by a chemical shift of 5°1 eV in b5c Lebel. This Nb3 d 5/□ is 207, 4 e V,
The binding energy of 210°2'eV at N b 3 d S/2 is characteristic of N b 20 s. The oxide thickness tax can be estimated as in Equation 1.

ただし、λ。８とλ、はそれぞれ酸化物と金属における
電子の平均自由行程、Ｉ　ａｘと工、は積分強度ｎ、Ｘ
とｎ、はＮｂ原子密度、θはサンプル面からの検出角度
である。酸化物の厚さを計算するのに使用した電子の平
均自由行程は、ニオブで１．４０１１、Ｎｂ２Ｏ，で２
．４ｎｍである。すなわち、ｎｍ／ｎ、、＝２．６９゜ 方和式（１）によれば、６．６Ｘ１０−６Ｐａで２０分
間酸化した場合のＮｂ２Ｏ，層の厚さは３．５１ｍであ
る。However, λ. 8 and λ are the mean free path of electrons in oxides and metals, respectively, I ax and λ are the integrated intensities n, X
and n is the Nb atom density, and θ is the detection angle from the sample surface. The electron mean free path used to calculate the oxide thickness is 1.4011 for niobium and 2 for Nb2O.
．． It is 4 nm. That is, nm/n, , = 2.69° According to the equation (1), the thickness of the Nb2O layer when oxidized at 6.6×10 −6 Pa for 20 minutes is 3.51 m.

良好な実施例のバリエーションでは、様々な厚さく０．
５ｏｍ、ｌｎｍ、２ｏｍ）のセリウム保護層を同じ酸化
処理にかけたとき、同じ量のＮｂ２Ｏ，が生成する。セ
リウムの触媒作用は、厚さが０．５〜２ｏｍの範囲では
その厚さによって変化しない。Variations of the preferred embodiment include various thicknesses of 0.
When a cerium protective layer of 5 ohm, 1 nm, 2 ohm) is subjected to the same oxidation treatment, the same amount of Nb2O, is produced. The catalytic action of cerium does not change depending on the thickness within the range of 0.5 to 2 om.

２５ｏｍのニオブをＱ、５ｏｍのセリウムで被覆して酸
素の代りに６．６Ｘ１０−’ＰａのＨ２０蒸気に２０分
間暴露しても、Ｎｂ２Ｏ，は生成されない。Even if 25 ohm niobium is coated with Q, 5 om cerium and exposed to 6.6 x 10-'Pa H20 vapor instead of oxygen for 20 minutes, no Nb2O, is produced.

これらの結果は、純粋な酸素中で酸化を行なう場合に表
面にＣｅ２Ｏ，とＣｅＯ２の混合物が形成されることを
確認するものである。These results confirm that a mixture of Ce2O and CeO2 is formed on the surface when oxidation is carried out in pure oxygen.

第４図は、酸素に暴露させる前（ａ）と後（ｂ）の保護
層のＣａ４ｄレベルを示すものである。金属セリウム相
は３価（ライ。ベール及びシー、ツアシェー、フィジカ
ル・レビュー・レター（Ｐｈｙｓ、Ｒｅｖ。Figure 4 shows the Ca4d level of the protective layer before (a) and after (b) exposure to oxygen. The metallic cerium phase is trivalent (Rei. Beer and C., Zuscher, Physical Review Letters (Phys, Rev.

Ｌｅｔｔ、、Ｖｏｌ、３９．ｐ、９５６．１９７７）を
参照のこと）であるが、酸化されたセリウムは、３価と
４価の両方を示す。水蒸気中で酸化を行なう場合、Ｃｅ
４ｄスペクトルで４価セリウムの証拠は見つからず、ニ
オブはセリウムの下では酸化しない。セリウムの触媒作
用は、表面酸化中の（３価から４価への）原子価の変化
に関係しているようである。ＣｅＯ２は、炭化水素の酸
化など酸化反応での触媒作用が大きいことがわかってい
る。その場合は、３価から４価へと原子価が変化しやす
いこととＣｅ　Ｏ。Lett, Vol. 39. p. 956.1977), but oxidized cerium exhibits both trivalent and tetravalent valence. When oxidizing in water vapor, Ce
No evidence of tetravalent cerium was found in the 4d spectrum, and niobium does not oxidize under cerium. The catalytic effect of cerium appears to be related to the change in valence (from trivalent to tetravalent) during surface oxidation. CeO2 is known to have a strong catalytic effect in oxidation reactions such as oxidation of hydrocarbons. In that case, the valence of CeO is likely to change from trivalent to tetravalent.

中での酸化移動度が大きいことがともによく反映されて
いる。ＣｅＯ２は酸素イオンの伝導体であり、多分結晶
状態でよりも無定形の場合の方がその作用が強いと思わ
れる。Both of these clearly reflect the large oxidation mobility within. CeO2 is a conductor of oxygen ions, and its effect is probably stronger in the amorphous state than in the crystalline state.

低温で形成される酸化物膜は無定形であることがわかっ
ている。Ｎ　ｂ　２０　ｓなどそれらの一部は網状構造
を形成する。小さいが緊密に結合されたカチオンよりも
大きな酸化イオンの方が網状通路を通りやすく、したが
ってこれらの酸化物膜は酸素イオン拡散によって成長す
る。It is known that oxide films formed at low temperatures are amorphous. Some of them, such as N b 20 s, form a network structure. Large oxide ions pass through the network channels more easily than small, tightly bound cations, so these oxide films grow by oxygen ion diffusion.

酸化の際に発生しイオン拡散を促進するモット（Ｍｏｔ
ｔ）電位はニオブよりもセリウムの方が大きいので、セ
リウムの方がニオブよりも酸化しやすい。表面の酸化さ
れたセリウムは、Ｃｅ　Ｏ，を大きな割合で含んでおり
、これはニオブでＣｅ２Ｏ３に還元できる。１モルの酸
素形成に関するＮｂ２Ｏ５の分解熱は１４６．８Ｋｃａ
Ｑであるが、ＣｅＯ２のそれは僅か１２５ＫｃａＱであ
るためである。（Ｃｅ２０３の分解熱は３０５ＫｃａＱ
なのでニオブはＣｅ２Ｏ３を還元できない。）酸素暴露
を続けると、酸素をニオブに与えたＣｅＯ２は表面で再
酸化し、ニオブがさらに酸化するための酸素イオンを供
給する。Mot is generated during oxidation and promotes ion diffusion.
t) Since the electric potential is greater for cerium than for niobium, cerium is more easily oxidized than niobium. The oxidized cerium on the surface contains a large proportion of Ce2O, which can be reduced to Ce2O3 with niobium. The heat of decomposition of Nb2O5 for the formation of 1 mole of oxygen is 146.8 Kca
Q, but that of CeO2 is only 125 KcaQ. (The heat of decomposition of Ce203 is 305KcaQ
Therefore, niobium cannot reduce Ce2O3. ) As the oxygen exposure continues, the CeO2 that has donated oxygen to the niobium reoxidizes at the surface, providing oxygen ions for further oxidation of the niobium.

第二の実験では、６．６　Ｘ、１０−’Ｐ　ａの酸素圧
力でのニオブの触媒酸化の反応速度論を研究するため、
０．９ｏｍのセリウムで被覆した、新しく付着させた５
０ｏｍのニオブの膜を使って、１分間から７時間暴露後
にＸＰＳスペクトルを取った。１分間暴露（３Ｌ）では
、表面のセリウムがまず酸化されるため、スペクトルは
Ｎｂ２Ｏ５を示さなかった。９Ｌの酸素暴露を示す、３
分後にとった次のスペクトルは、既に１．９ｏｍのＮｂ
２Ｏ，が形成されていることを示した。このことを、９
Ｌ暴露で非常に少量のＮｂＯとＮｂＯ，が形成され、Ｎ
ｂ２Ｏ，、は検出されない、触媒なしてのニオブの酸化
と比較すべきである。In the second experiment, to study the kinetics of catalytic oxidation of niobium at an oxygen pressure of 6.6 X, 10-'Pa,
Freshly deposited 5 coated with 0.9om cerium
XPS spectra were taken using a 0 om niobium film after exposure for 1 minute to 7 hours. At 1 minute exposure (3 L), the spectrum did not show Nb2O5 because the cerium on the surface was oxidized first. 3, indicating 9L of oxygen exposure
The next spectrum taken minutes later was already 1.9 om Nb
It was shown that 2O, was formed. 9.
Very small amounts of NbO and NbO are formed upon exposure to L, and NbO,
b2O,, is not detected, which should be compared to the oxidation of niobium without catalyst.

第５図は、（方程式１で計算した）Ｎｂ２ｏ、、層の厚
さを酸化時間の対数の関数として示したものである。図
から、酸化時間が大体４０分頃までは急速に成長するこ
とがわかる。これは１２０Ｌの酸素暴露に相当する。こ
こですでに４ｏｍの純粋なＮｂ２Ｏ，が形成されている
。このことを、１２０Ｌの酸素に暴露したとき０．６ｏ
ｍのＮｂ’Ｏ＋ＮｂＯ２の上にＮｂ２Ｏ，が０．Ｏ５ｎ
ｍしか形成されない、触媒なしのニオブ酸化と比較すべ
きである。FIG. 5 shows the thickness of the Nb2o layer (calculated using equation 1) as a function of the logarithm of the oxidation time. From the figure, it can be seen that growth occurs rapidly until the oxidation time is about 40 minutes. This corresponds to 120L of oxygen exposure. Here, 4 om of pure Nb2O has already been formed. This corresponds to 0.6o when exposed to 120L of oxygen.
Nb2O, on top of Nb'O+NbO2 of m, is 0. O5n
Comparison should be made with the uncatalyzed niobium oxidation, where only m is formed.

速い成長は両対数表示（挿入図）で１／３の勾配を特徴
とし、それが対数時間依存関係を特徴とするゆっくりし
た成長に変わる。７時間（１，２６ＯＬ）後の厚さは４
．８ｏｍである。ニオブの非触媒酸化では、ゆっくりし
た成長体制しかみられない。Fast growth is characterized by a slope of 1/3 in logarithmic representation (inset), which gives way to slow growth characterized by a logarithmic time dependence. Thickness after 7 hours (1,26OL) is 4
．． It is 8 ohm. Noncatalytic oxidation of niobium shows only a slow growth regime.

Ｎｂ２Ｏ，の生成は、対数的時間依存関数を特徴とする
。１２６０Ｌの酸素に暴露したとき、０．６ｏｍのＮｂ
Ｏ＋ＮｂＯ□の上にＮｂ２Ｏ５が０．２ｏｍしか形成さ
れない。The generation of Nb2O, is characterized by a logarithmic time-dependent function. 0.6om Nb when exposed to 1260L of oxygen
Only 0.2 om of Nb2O5 is formed on O+NbO□.

触媒酸化の実験から、酸素分圧が増大すると酸化物層の
厚さも増加することがわかっている。例えば、６．６Ｘ
１０−’Ｐａの酸素圧力で２０分間酸化すると、厚さ３
０５ｎｍのＮｂ２Ｏ，となるが、１．３２Ｘ１０’Ｐａ
で同じ時間酸化すると６゜７ｎｍのＮ　ｂ　２０　ｓが
できる。第６図を参照のこと。Catalytic oxidation experiments have shown that as the oxygen partial pressure increases, the thickness of the oxide layer also increases. For example, 6.6X
When oxidized for 20 minutes at an oxygen pressure of 10-'Pa, a thickness of 3
05nm Nb2O, but 1.32X10'Pa
When oxidized for the same period of time, N b 20 s with a thickness of 6°7 nm is produced. See Figure 6.

酸化温度を室温からやや高い温度まで上げると、酸化物
の厚さは指数関数的に増大する。As the oxidation temperature is increased from room temperature to slightly higher temperatures, the oxide thickness increases exponentially.

」二連のように、セリウムの触媒作用により、よく制御
されたＵＨＶ状態の下では、かなりの星のＮ　ｂ　２０
　ｓが成長できる。純粋なニオブを大気圧で同等の暴露
時装置いた場合に得られるよりも、厚さがずっと大きく
なる。しかし、触媒を使って固体を酸化することの利点
は、より短い時間で速度間約変化と平衡に達するだけで
なく、この触媒によってもたらされる平衡状態が化学量
論の点で非平衡状態よりも完全な（低次酸化物が形成さ
れない）ことである。セリウム触媒の重要な特徴は、表
面酸化中にその原子価が３価から４価に変わることであ
ることがわかった。” Under well-controlled UHV conditions, due to cerium catalysis, significant stellar N b 20
s can grow. The thickness is much greater than would be obtained with an equivalent exposure device of pure niobium at atmospheric pressure. However, the advantage of using a catalyst to oxidize solids is not only that it reaches equilibrium with a change in rate in a shorter time, but also that the equilibrium state brought about by this catalyst is more stoichiometrically than a non-equilibrium state. complete (no lower oxides are formed). It was found that an important feature of the cerium catalyst is that its valence changes from trivalent to tetravalent during surface oxidation.

原子価が３価から４価に変化する、プラセオジムやテル
ビウムなど他の希土類の触媒作用も、セリウムと類似し
ている。制御された状態で酸化して保護／絶縁酸化物層
を形成することができる、アルミニウム、ハフニウム、
チタン、ジルコニウム、タンタル基板材料も、ある種の
用途では、ニオブの代りに金属または合金として使える
。シリコンは、１０００℃のような極めて高い酸化温度
でしか有用な絶縁厚さのＳｉＯ□酸化物層を形成しない
が、上記の触媒を使うと、室温前後の温度で酸化するこ
とができる。酸化物パターンは、酸化の前にマスキング
したまたはエツチング法を使って触媒をパターン付けす
ることによって生成できる。The catalytic behavior of other rare earths, such as praseodymium and terbium, whose valence changes from trivalent to tetravalent, is also similar to that of cerium. Aluminum, hafnium, which can be oxidized in a controlled manner to form a protective/insulating oxide layer.
Titanium, zirconium, and tantalum substrate materials can also be used as metals or alloys in place of niobium in certain applications. Silicon, which forms SiO□ oxide layers of useful insulating thickness only at extremely high oxidation temperatures, such as 1000° C., can be oxidized at temperatures around room temperature using the catalysts described above. Oxide patterns can be produced by patterning the catalyst using masked or etched methods prior to oxidation.

本発明を良好な実施例す外わち、様々な厚さ及び様々な
材料を用いたセリウム触媒によるニオブ酸化について説
明してきたが、当業者なら理解できるように、本発明の
精神と範囲から外れることなく、原子価が変化するその
他の希土類や各種の酸化可能な基板材料と合金を使用す
ることができる。While this invention has been described as a preferred embodiment, ie, cerium-catalyzed niobium oxidation using various thicknesses and various materials, those skilled in the art will appreciate that the invention falls outside the spirit and scope of the invention. Other rare earths of varying valence and various oxidizable substrate materials and alloys can be used without the need for oxidation.

［発明の効果］ 本発明の効果は、高品質の絶縁層を高温を必要とせずに
形成することができることである。さらに、高品質の絶
縁層の有効パターンを高温を必要とせずに、触媒パター
ンがそのまま受け容れできるかまたは容易に取り除ける
ような形で提供することもできる。[Effects of the Invention] An effect of the present invention is that a high-quality insulating layer can be formed without requiring high temperatures. Additionally, an effective pattern of high quality insulating layers can be provided without the need for high temperatures and in such a way that the catalyst pattern can be accepted or easily removed.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は、本発明の良好な実施例にもとづく集積回路加
工中間体の概略図である。 第２図は、次のものの合成ＸＰＳスペクトルである。 （ａ）　新しく蒸着させた２５ｎｍのニオブは、結合エ
ネルギー２０２．３ｅＶのＮ　ｂ　３　ｄ　Ｓ／２ピー
クと２０５．１ｅＶのＮｂ５ｄ３．□ピークとクリーン
金属の電子レベルしか示さない。 （ｂ）　３００　Ｋで６．６Ｘ１０−’Ｐａの純粋酸素
に２０分間暴露させた後、Ｎｂ５ｄレベルは、少量の低
次Ｎｂ酸化物の形成しか示さな（１６ 第３図は、０．６ｎｍのセリウムで覆った新しく蒸着さ
せた２５ｎｍのニオブのＸＦＩＳスペクトルである。 （ａ）　酸素に暴露する前のＮｂ５ｄレベル。 （ｂ）　３００　Ｋで６．６Ｘ１０−’Ｐａの酸素に２
０分間暴露した後の３ｄレベル。Ｎｂ５ｄレベルが、５
．１ｅＶ化学シフトすることを特徴とするＮｂ２Ｏ，が
、かなりの量形成されたことを示す。 第４図は、酸素に暴露する前（ａ）と（ｂ）のセリウム
保護層の合成ＸＰＳスペクトルである。金属セリウムは
３価だけであるが、酸化相はその他にＣｅ’＋化学種を
示す。 第５図は、Ｎｂ２Ｏ５層の厚さを３００にでの酸化時間
の対数の関数として示した図である。この図は、大体４
ｎｍの厚さまで両対数表示（挿入図）で１／３の勾配を
特徴とする速い成長を示し、それが対数的時間依存関係
を特徴とするゆっくりした成長に変わることを示す。 第６図は、ニオブ上にセリウム、プラセオジム及びテル
ビウム触媒を使った場合のＮｂ２Ｏ，酸化物の厚さの、
酸素圧力の対数に対する依存関係を示す図である。 出願人　インターナショナル・ビジネス・マシーンズ・
コーポレーション 復代理人　弁理士　合　１）　潔 第１図 ２００　２０４　２０８　２１２　’　ＥＢ（ｐＶ）　
第８図FIG. 1 is a schematic diagram of an integrated circuit processing intermediate according to a preferred embodiment of the present invention. FIG. 2 is a composite XPS spectrum of: (a) Freshly deposited 25 nm niobium has a N b 3 d S/2 peak with a binding energy of 202.3 eV and a Nb 5 d 3 . □ Shows only peak and clean metal electron levels. (b) After 20 min exposure to pure oxygen at 300 K and 6.6 x 10-'Pa, the Nb5d level shows only a small amount of lower-order Nb oxide formation (16 Figure 3 shows that the 0.6 nm XFIS spectra of freshly deposited 25 nm niobium coated with cerium. (a) Nb5d level before exposure to oxygen. (b) 2 to 6.6 x 10-'Pa of oxygen at 300 K.
3d level after 0 minute exposure. Nb5d level is 5
．． This indicates that a significant amount of Nb2O, characterized by a 1 eV chemical shift, was formed. FIG. 4 is a composite XPS spectrum of the cerium protective layer (a) and (b) before exposure to oxygen. Metallic cerium is only trivalent, but the oxidized phase additionally exhibits Ce'+ species. FIG. 5 shows the thickness of the Nb2O5 layer as a function of the logarithm of the oxidation time at 300 nm. This figure is approximately 4
We show a fast growth characterized by a slope of 1/3 in double logarithmic representation (inset) up to a thickness of nm, which changes to a slow growth characterized by a logarithmic time dependence. Figure 6 shows the thickness of Nb2O oxide when using cerium, praseodymium and terbium catalysts on niobium.
FIG. 3 is a diagram showing the dependence of oxygen pressure on the logarithm. Applicant International Business Machines
Corporation Sub-Agent Patent Attorney 1) Kiyoshi 1 Figure 200 204 208 212' EB (pV)
Figure 8

Claims (1)

【特許請求の範囲】[Claims] 酸化中の原子価の増大に関係する触媒作用をもつ希土類
の１乃至１０単分子層の非常に薄い層を付着させること
、及び室温またはそれよりもやや高い温度で望みの厚さ
まで酸化物を成長させるのに必要な時間、それに必要な
酸素分圧で酸素に暴露することを含む、固体表面に酸化
物層を形成する方法。Depositing very thin layers of 1 to 10 monolayers of rare earths with catalytic properties that are responsible for the increase in valence during oxidation, and growing the oxide to the desired thickness at room temperature or slightly higher. A method of forming an oxide layer on a solid surface, the method comprising exposing it to oxygen for a period of time and at a partial pressure of oxygen necessary to cause the formation of an oxide layer on a solid surface.
JP60045024A 1984-05-15 1985-03-08 Method for catalytic oxidation of solid substance Expired - Lifetime JPH0638524B2 (en)

Applications Claiming Priority (2)

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US06/610,355 US4526629A (en) 1984-05-15 1984-05-15 Catalytic oxidation of solid materials

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO1994028579A1 (en) * 1993-05-25 1994-12-08 Tadahiro Ohmi Method of forming insulating oxide film and semiconductor device

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US4735921A (en) * 1987-05-29 1988-04-05 Patrick Soukiassian Nitridation of silicon and other semiconductors using alkali metal catalysts
US4806505A (en) * 1987-10-30 1989-02-21 Regents Of The University Of Minnesota Samarium- and ytterbium-promoted oxidation of silicon and gallium arsenide surfaces
US6146135A (en) * 1991-08-19 2000-11-14 Tadahiro Ohmi Oxide film forming method
US5427630A (en) * 1994-05-09 1995-06-27 International Business Machines Corporation Mask material for low temperature selective growth of silicon or silicon alloys
JP2937817B2 (en) * 1995-08-01 1999-08-23 松下電子工業株式会社 Method of forming oxide film on semiconductor substrate surface and method of manufacturing MOS semiconductor device
US6707647B2 (en) * 2001-01-29 2004-03-16 International Business Machines Corporation Magnetic head with thin gap layers
JP2003073794A (en) * 2001-06-18 2003-03-12 Shin Etsu Chem Co Ltd Heat-resistant coated member
DE10304756B4 (en) * 2003-02-05 2005-04-07 W.C. Heraeus Gmbh Oxygenated niobium wire
DE102004032128B4 (en) * 2003-10-17 2010-10-14 W.C. Heraeus Gmbh Metallic material, method of manufacture and use
US7615385B2 (en) 2006-09-20 2009-11-10 Hypres, Inc Double-masking technique for increasing fabrication yield in superconducting electronics
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US4001317A (en) * 1974-07-22 1977-01-04 Standard Oil Company Process for the oxidation of olefins using catalysts containing various promoter elements
DE2555187A1 (en) * 1975-12-08 1977-06-16 Siemens Ag Semiconductor with coating of inorg. insulation and metallised layer - has metallised layer surface oxidised by simultaneous application of heat and oxidising medium under press.
JPS5610334A (en) * 1979-07-06 1981-02-02 Toyota Motor Corp Catalyst for cleaning up exhaust gas and manufacture of said catalyst
US4341662A (en) * 1980-04-11 1982-07-27 Pfefferle William C Method of catalytically coating low porosity ceramic surfaces
JPH0722183B2 (en) * 1981-10-09 1995-03-08 富士通株式会社 Method for manufacturing dielectric layer for semiconductor device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994028579A1 (en) * 1993-05-25 1994-12-08 Tadahiro Ohmi Method of forming insulating oxide film and semiconductor device

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JPH0638524B2 (en) 1994-05-18
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EP0161619B1 (en) 1992-04-15
US4526629A (en) 1985-07-02

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